Rutile seed manufacture



Patented Nov. 22, 1949 RUTIIJEfSEED MANUFACTURE rLeif Aagaard, Amherst, Va.,-ass'i-gnor,"-by mesne assignments, to "AmericamGyanamid fiompa'ny,

a-corporation of, Maine :iNo Drawing. "Application January 31, .1942, "Serial No. 428,997

This invention relates -to :the preparation zo'i rutile titanium 'dioxideizby rthe calcinati'onlzof :an anatase precipitate-under controlled :conditions, "and aims tc-provideawn-especially effective-.-meth- -od of producing rutile seeds.

Titanium dioxide,=within the lath-irt-y yearssince its introduction as a -:pigment, .has -made.1such rapid strides that it has become the "outstanding white pigment used in -the--.'coating 'and allied industries; this popularity --is =due mainly 'to its whiteness, stability, high *hiding :apOWeI, ":higher tinting strength, and ready dispersibilt-y in 1 ve--' hicles. Itis prepared largely by the hydrolysis, under careful-ly controlledconditions, of titanium sulfatesolutionscontaining iron, prepared by digestion of *il'menite (a "native -'-'ferrous =titanate) with sulfuric acid, followed lay-reduction of all ferric iron toferrous iron, removal of a part ofthe iron bycrystallization as ferrous sulfate, clarification and adjustment of concentration; the hydrolysate is :calcined; together :with conditioning agents, to :produce the "desired "white pigment.

The titanium dioxideso produced hasrbeen predominantly of anatase crystal structure, one of the three crystal modifications "(anatase,' brook- .ite, rutile) in which .titanium "dioxide :occurs. 'Theart has'known-jthatitherutile structure, on accountof its higher,refractiveindex, shoul'd'have higher hiding poweriandfltinting stren ththan .the .anatase. structure, but rutiletitanium. dioxide having better hiding power and "tinting strength has .not -been available commercially 'because there has been 1no ,,process ;for"its production at .acost comparablewith.thatcf producinganatase.

vIt v.is .well known that the .uncalcine'dprecipltate, obtained .by .theihydrolysis of. titanium sul- .iate, has the crystalsstructure of.-anatase which .is further developed upon-calcinationas thecombined water andthe combined and/or adsorbed acidare expelled. ,.'It,,is...also; known,thatlthe unica'lcined precipitate .obtained .by the .1 hydrolysis 20f titanium .salts of monobasic .acids such as. 'for. example, .titanium chloride, has the crystal structure .of ,rutile which is Ifurther jdevelopefd .upon calcination. .ltiszalsouknown thattheanatase structure obtainedby .the hydrolysis .of .ti- .tanium .sulfate. can be converted to rutile by continued calcination at.. a yeryihightemperature. .Such .calcination, .howeuer, causes ..crystal growth. and. discolorationwhich:resultsiima .prodduct undesirablevfor names .a white pigment. .No {process inwhichithe .titaniumis, precipitated from salts f monobasic acids u's economically vcom- ;petitive withtheisulfate processs'largelylbecause ture.

.5-Claims. (ClLi 23- 202) v 6a of higher acid cost'and the corrosion problems introduced by the 1 use of these monobasicacids.

In co-pendingpatent application Serial Number 422,104, filed December 8,1941,'now abandcned, it is-proposed'to convert-an anatase precipitate, obtained by the hydrolysis of titanium sulfate solutions, to rutile, by first roasting *the precipitate in the presence of an alkali metal salt, Washing the roasted precipitate substantially free of alkalimetal-salt, and then calcining in the presence "of a small amount of 'a rutile seed consisting of calcined-titanium dioxide, having the crystal structure of rutile, :or consisting of an uncalcinedprecipitate obtained by the hydrolysis of an aqueous solution or a monobasic acid compound of titanium. 'It"is disclosed 'that'the'rutile seed may be added eitherprior to or after the roasting'operation.

In co-pending patent applicationSerial Num- 'ber 422,082, filed December -8, 1941, now aban- 'doned, it is proposed to convert an anatase-pre- .cipitate, obtained by the hydrolysis of' titanium sulfate solutions, to rutile by-calciningin'thepresence of a small amount of--an'alkali metal comrpoundcandla small amount of a rutile-seedconsisting of :calcined titanium ,dioxide having "the crystal structure .of .rutile or consisting :of 5311 uncalcined precipitate'robtained by hydrolysis ;of .an aqueous solutionflofna-monobasic acid-compoundof titanium.

In co-pending Ross and ,Tanner application, Serial Number 429,118, filed January 31, 1942, it is proposed to prepare .a rutile seed for use in the production of titanium dioxide of rutile crystal structure by .treating an 'alkali metal vtitanate wit-h'limited quantities of a monobasic acid, such as hydrochloric acid. The titanate is treated with hydrochloric acid .in-sufficient quantity "to neutralize the :sodium zoxide, andin ,suflicient excess r'forsabout 20% to aboutv50%cof :theory for theformation ,of-titanium tetrachloride. About 25% of the theoretical 'quantity for titanium tetrachloride ,after neutralizing the'sodium oxideisapreferred. The hydrochloric acid slurry is diluted with water and boilediorabout :one hour. Nitric acid .or other monobasic acids may be usedin ,pl'aceof hydrochloricacid. The amount of said {acid usedis insuflicient for complete solution of titanium. The .titanium, however, during the boiling period, is transferredto a desirable rutile seed for. use in .converting'anatase structure to rutile .structure during calcination. some such seeds. prepared by us haveshowniby X-rayjan alysissubstantially completerutilenstruc- In that above-identified application, the alkali metal titanate is prepared from a sulfate hydrolysate which is boiled for several hours to obtain precipitation.

I have now discovered that the rutile seed can be obtained more effectively by the treatment of orthotitanic acid (Ti(OH)4) with an alkaline compound of an alkali metal to form an alkali metal titanate, followed by treatment of the alkali metal titanate thus formed with a monovalent acid. As compared with the former method of preparing the titanate, my method is more rapid and less expensive, and the resultant seed is somewhat more effective in rutile conversion.

In a preferred procedure, an aqueous pulp of orthotitanic acid prepared in any manner whatsoever is treated with from about 0.8 to about 1.5 parts of sodium hydroxide to one part of anhydrous titanium dioxide. The mixture may be stirred cold, or heated for from about one to about six hours at a temperature of about 80 C. to 100 C. One and one-quarter parts of sodium hydroxide to one part of titanium dioxide is the preferred amount. Solid fiake sodium hydroxide may be mixed with the concentrated aqueous pulp of the orthotitanic acid and then heated without further agitation. A eoncentrated solution of sodium hydroxide may be mixed with the orthotitanic acid pulp and heated while continuously stirring. Depending upon the 7 amount of sodium hydroxide used and also upon the concentration of the sodium hydroxide and orthotitanic acid mixture, the temperature may vary considerably up to and above 100 C., even up to the fusion point, if desired.

While orthotitanic acid prepared in any manner whatsoever may be used, I prefer, for economic and other reasons, to use an orthotitam'c acid prepared by precipitation from a clarified basic sulfate solution of ilmenite ore, from which a part of the iron has been removed by crystallizing as ferrous sulfate. A typical analysis of such a solution is as follows:

Specific gravity 1.42 Titanium dioxide (TiOz) per cent 10 Ferrous sulfate (F8804) do 10 Sulfuric acid (H2804) combined with titanium dioxide per cent 18 Methods for preparation of the orthotitanic acid are given in Examples 1 and 2.

Example 1 about one hour, and with good agitation. The

gypsum (CaSO4-2H2O) thus formed as filtered out and washed with about 1500 cc. of cold water. The filtrate containing the titanium and iron is then diluted to about liters.

2000 cc. of an aqueous slurry containing grams of hydrated lime, at a temperature of about 30 C., is then slowly added to the 15 liters containing the titanium and the iron, at a temperature of about 30 C. during about one-half hour and with good agitation. The pH of the precipitated slurry is about 2.7, and about 90% of the titanium has been precipitated as orthotitanic acid. The orthotitanic acid is filtered out and washed substantially free of iron and calcium.

Example 2 1500 cc. of an aqueous slurry at a temperature of about 30 C., and containing 150 grams of hydrated lime, are added to 1060 cc. of the basic sulfate solution containing 150 grams of titanium dioxide at a temperature of about 30 C., during about one hour, and with good agitation. The gypsum (CaSOi-ZHzO) thus formed is filtered out and washed with about 1500 cc. of cold water. The filtrate containing the titanium and iron is then diluted to about 15 liters.

2000 cc. of an aqueous solution containing 64 grams of calcium acetate at a temperature of about 30 C. is then slowly added to the 15 liters containin the titanium and the iron, at a ternperature of about 30 C., during about one-half hour and with good agitation. The pH of the precipitated slurry is about 2.0, and about 90% of the titanium has been precipitated as orthotitanic acid. The calcium acetate causes the precipitation of the titanium at a relatively low pH, and thus avoids the co-precipitation of metallic impurities such as vanadium and chromium. The orthotitanic acid is filtered out and washed substantially free of iron and calcium.

I prefer to prepare the calcium acetate solution as follows:

300 cc. of an aqueous solution containing 50 grams of acetic acid is added to 300 cc. of an aqueous slurry containing 30 grams of hydrated lime. To the solution thus formed is then added, while stirring, an aqueous slurry of hydrated lime, until a slight precipitate is formed, This addition of lime precipitates metallic impurities in the calcium acetate solution. The solution is filtered and diluted to 2000 cc.

The orthotitanic acid prepared in accordance with Example 1 or Example 2 is then treated with an alkaline alkali metal compound, such as sodium hydroxide, to form an alkali metal titanate. To the sodium titanate thus formed, water, which causes some hydrolysis of the titanate, and consequent formation of hydrated titanium dioxide and/or other titanate or titanates, is added. The solids are washed by decantation, and then filtered and washed. The washed solids contain, by analysis after calcination, about titanium dioxide, and about 15% sodium oxide. No attempt is made herein to ascribe any definite composition to the original titanate formed, nor to the solids remaining after treatment with water and washing.

The washed solids are treated with hydrochloric acid in sufficient quantity to neutralize the sodium oxide, and in sufficient excess for about 20% to about 50% of theory for the formation of titanium tetrachloride. About 25% of the theoretical quantity for titanium tetrachloride after neutralizing the sodium oxide is preferred. The hydrochloric acid slurry is diluted with Water, and boiled for. about one hour. Nitric acid or other monobasic acids may be used in place of hydrochloric acid, Theamount of acid used is ordinarily insufficient for complete solution of titanium, although peptization generally occurs. The titanium, however, during the boiling period, is transferred to a desirable rutile seed for use in converting anatase structure to rutile structure during calcination. Some such seeds prepared byus have shown by X-ray analysis substantially complete rutile structure.

If desired, the titanate may be treated directly with the monobasic acid, thus omitting the water treatment. I prefer to use the water treatment, however, since it eliminates a large amount of the any'stagefiwthe process prior to the fihal wasliie m:-

ihg' before calc-inat'ion: or it mawbe flocculated' bwadir'isting the slurry teap]?! of" from" about? 4-:5 to '7lfi by-neuti-aliz' ing w-i'th analkaline reagents such as sodium carbonate filtered; washed subwstantiallwfree of" chlorides; and" then mixedfwitli arr 'uncalci-ned liydrated titanium dioxide preeipi tater .oliitaineelbw hydrolytic i precipitationfrontafiftanium'sulfate sol-utiorrat"anystage in tl ie-proc essprior' to'calcination;

special' 'rutile seed isfextremely finaw divf see; which probably accounts"foritsexceptionaf activity:- By-irs use--as;a-seedj eventir'r-relatively small amounts; substantml'ly-complete conversion torutile may be obtained under ordinary calcina tiorrconditions.

The'amountbf intilezseed usedmaywary wid' limits: Wl'iil'e" genera'l'weprefrtn-use' about 5 based upon the. total. weightbf the tita' nium dioxide calcined; smaller andilargenpercentsolids-momenta Tojthiaaqueeussslurm issaddzd offifiakerssodiumrhydroeride whileestiifs continuously: The mixtureeisrthemheatecbl for about two hours at'aacetempezature'aofsabouti 855% (3;. W290? '51, while: continuously; stirring,- .and

artzzmwnstantiminmea The titanate thusziormedi. i$fiIUBfEIh washedislibstantia'llm free: of? sui-'ifates. The filter cake is slurried lil :248-Cfi;;:.0 commercial B. hyditoelnloric acid, diluted with 1350 cc. of water,.,and;boiled..at constant volume forafioutlone houn;

Emma 4r Tfi'ef'ortliotitarrio'acidi of Example 11' or Ekamp'i 271s: adjusted wi'tlizwater to: about? I8't% calcined solids? contentz. To" use aqueous slurry".- is" added 1'357grams" ofi'flake" sodiiumhydroxide; while ring'contmuou'slyr. 'I'lrecmiic'ture is thent'heated: for aboutttwo hours at atemperature'ofabout 85 C; to 9 YCiinw-hile stirring continuously; and at"amonstantimliinre:- Thexitanate thus formed. is; filtered andflwashed; substantially; free ofsul fates. The; filter-(cake is. slurriedin 248 cc: of?" commercial T20? B." hydrochloric acid; diluted Ifl1cc;..of;water; ,andboild at constant 1 volume r611. afioutsoneyliour; The '.seed--.slurry., is .cooledltd 60? (Land adiustedto' a. pH of..5.1'f.by, theadditiorr ofilab'ouii23'0. cc; .ofi"a.20l%' solutibnroflsodium car.-= bonate. At'thi's pHtl'ie seed is sufli'ci'ntly. 116601]:

ages maybe used: Evenzas' little as I'% orlssisfiiiflatedie. herflltereds. ltisifilteredi and;.waslied effective: Obviously there is no upper. limit.

Theactualiamount'of rutil'e. seed used depends uppnithe .amount'ofirutileconversion desired; and al'soupon'the; desired other properties of the fin i'shed "pigment, such as color; and;softness. use of 5% or. more seed": induces conversion .to rutilie"'*ata;lowe1:'temperature'or'in a shorter time, or-b'oth; and-thereby produces a pi'gmentof *rutil structure'which'has a' coIor higher irrtotal bright;

substantially of; sodium and chloride i'onse Example "5 The orthotitanic acid "of Example for Ekampl The 3&2 is adjusted with wat'ei to about, 18% calcined solids; content, Tea this aqueous slmrw isadded 135 gramss of 1flalce sodium.hyehuaxide;whileestirsring: CQHfim-AOHSI'Ye 'Ihe mixture-sis them-heated fiery-about 'itwoehonrss at an temperature ofrabout ness and which" dispersestfmore readily? when asser tor-90 6.,- wh uezstirrmg'eontinuousimami groundin vehicles;

It is'desired to place no1limit upon1 theirutil conversion'obtained. For. certain purposes'relae tively small. conversionimay; be'. desiredj andlin "other casesia substantially?" complete conversion 45.: @gwatw;amfijbfledeat;mmtamwommeflmwwbgm may 'be desired For examp'le, it maybe dsir;

able to producea: pigment"-c'ontainingjfltmi rutile and85%'f anatase; era pigment" containinggQOVi:

rutile' and-'10 anatase:

Thehiding-power and? tinting: strength-- of. the 5'0 pigment produced, according to" our: process in creases proportionatelyas the conversionto'ruti'le increases;

A small amount of an-ironsalt; such as ferric ata :constant wolmne; titanateathus formed; isefilteredz; amzwasheds substantialiy fireezofr Sill-'2 fates-s Hie flit cakezzisrslurried 852cc. oft come memialrZFB nitric"acimvdilutediwi'tliiulafiwcez email-mun- Having? described2?mi inventiom and F given ex? samples ill ustratmg methods: for preparing: the" rutile-seed Fnow gi v'e examples illustrating the eonversion of anatase structure tos rt-Ftfle struc ammonium..Su1-fate, Ora.smau,amountsoflcopper, dratedtitanimndioxideprecipftate, obtainedby salt, suchas coppen'sulfate: which salts"- decom pose and form the oxides-'ofthe-"metals' uporrcal cination, may be added at some stage=prior to calcining to prevent bli iirrev or= graying of the color of the pigment during calcination: The

preferred amour-1t of iron sis from about .01 to: about" .O3%-,--ca1culatedas F6203; and based upon' the-.weightof thetita-nium dioxide: If theuncal cinedhyditated tit'anhumdioxidealready contains F hydrolytic precipitation fromatitanium sulfate solution; and containing ZUIYIgTHHTISlOf' titanium dioxide; ismiiredi warren grams-o1. the. neutralized and washew'seed of Example 4? containing; 6 grams of titaniumdioxide,,with 0.24 gram of ferric ammonium 'sulfateontaining .06: gram of ferriesoiddes.andswiirlmaiconeentratedzaauedusasolutio ieontainin gz gramszefifpotassiumzcarhons ates. Tliezmixtureiis fiedifiafidilmaStedfi-fili'Gfle" is correspondinglydess" than "the .0 1%- to 103%; so" that the calcined pigmentwill containfrom11-1 to-.0.3% FezO3.; Tliepreferred-amount of' 'copper' issfrom .0004%;to-.oo2"%"; calcuI'ated asCuO-L- Detailed" methods for; the" final preparatiorr of W my rutile seed are-givemirr Eiiamp les'-'3;-

andf5-t Example 3 Thezorthotitani'o-acid"ofExamplesr oi-mlxample of-eo e' cf B. hydrochloritryaacidiareiazdd'i ed; re irezzediouta'andiwasheei r The transformation to rutile, as determined by X-ray analysis, has been substantially complete.

The tinting strength of the hydroclassified and dry milled pigment is 1720.

Tinting strength evaluations are based upon an arbitrary scale in which present commercial titanium dioxide of anatase crystal structure has a value of 1250.

1 Example 7 A thoroughly washed aqueous pulp of an hy-' monium sulfate containing .04, gram of ferric.

oxide, and with 4.0 grams of potassium carbonate. The mixture is dried and roasted for one hour at a temperature of about 850 C.

The roasted product is milled and slurried in water. 85 grams of the hydrochloric acid suspension of Example 3 containing 6 grams of ti tanium dioxide are added. The mixture is fil tered and the filter cake is washed substantially free of alkali metal salts. The filter cake is then dried and calcined by slowly raising the tempera; ture from about 300 C. to about 975 C. during about five hours, and then holding at a temperature of about 975 C. to about 1000 C. for about two hours.

The transformation to rutile, as determined by X-ray analysis, has been substantially complete. The tinting strength of the hydroclassified and dry milled pigment is 1720.

Example 8 A thoroughly washed aqueous pulp of an hydrated titanium dioxide precipitate, obtained by hydrolytic precipitation from a titanium sulfate solution, and containing 200 grams of titanium dioxide, is diluted with water to a calcined solids content of and mixed with 85 grams of the hydrochloric acid suspension of Example 3, which contains 6 grams of titanium dioxide. The mix ture is filtered and washed until the filter cake is substantially free of chlorides. The filter cake is then mixed with a concentrated aqueous solution containing 0.24 gram of ferric ammonium sulfate, which contains .04 gram of ferric-oxide, and with a concentrated aqueous solution containing 0.41 gram of potassium carbonate, dried and calcined by slowly raising the temperature from about 300 C. to about 975 C. during about five hours, and then holding at a temperature of about 975 C. to about 1000 C. for about four hours.

The calcined pigment contains by X-ray analysis about 90% rutile. The tinting strength of the hydroclassified and dry milled pigment is 1700. I a Example 9 A thoroughly washed aqueous'pulp of an hydrated titanium dioxide precipitate, obtained by hydrolytic precipitation from a titanium sulfate solution, and containing 200 grams of titanium dioxide, is mixed with 125 grams of the neutralized, filtered and washed seed of Example 4, containing 10 grams of titanium dioxide, and with a concentrated aqueous solution containing 0.42 gram of potassium carbonate, and calcined for about two hours at a temperature of about 975 C. to about 1000 C.

: The calcined pigment contains by X-ray-analy-v sis about 90% rutile.' The tinting strength of the hydroclassified and dry milled pigment is 1700'.

8.. The color of the product is not quite as good as that of the products obtained in Examples 4, 5 and 6, due to the omission of the iron addition.

Example 10 A thoroughly washed aqueous pulp of an hydrated titanium dioxide precipitate, obtained by hydrolytic precipitation from a titanium sulfate solution, and containing 200 grams of titanium dioxide, is diluted with water to a calcined solids content of 20%, and mixed with grams of the nitric acid suspension of Example 5, containing 10 grams of titanium dioxide. The mixture is filtered, and the filter cake is washed substantially free of nitrates. The filter cake is then mixed with 0.24 gram of ferric ammonium sul-v fate containing .04 gram of ferric oxide, and with a concentrated aqueous solution containing 0.42 gram of potassium carbonate, dried and calcined by slowly raising the temperature from about 300 C. to about 975 C. during about five hours, and then holding at a temperature of about 975 C. to about 1000 C. for about three hours.

The transformation to rutile, as determined by I X-ray analysis, has been substantially complete.

The tinting strength of the hydroclassified pigment is 1720.

While a rather definite calcination schedule is indicated in the examples, this schedule may be varied considerably. In actual commercial operation the calcination may be continuous through a rotating horizontal kiln which is heated at the discharge end and in which therefore there is a gradual temperature change from one end of the kiln to the other.

My calcined pigment, obtained in accordance with any of the modifications of the invention, may be either simply dry milled or wet milled, hydroclassified, treated with the usual reagents, filtered, dried and disintegrated in accordance with the present known procedures for produc ing the commercial titanium dioxide pigments having the anatase crystal structure.

My finished pigment has many desirable properties, such as good resistance to chalking, excellent resistance to discoloration in white baking enamels, etc., but is characterized in the main by its exceptional hiding power and tinting strength. The hiding power and tinting strength of the product in which the conversion to rutile has been substantially complete is in the neigh borhood of 40% higher than that of present commercial titanium dioxide having the anatase crystal structure. When the conversion to rutile has been less, the advantage in hiding power and tinting strength is correspondingly less.

I claim:

1. A process for producing rutile seed for use in the production of titanium dioxide having rutile crystal structure, which comprises treating orthotitanic acid with an alkaline alkali metal compound to form an alkali metal titanate, and treating the titanate with a monobasic acid in suficient amount to completely convert the alkali metal content to the salt of the monobasic acid and to theoretically convert about 20% to 50% of the titanium content to the salt of the mono-. basic acid, and heating the resultant mixture, whereby the titanium content is substantially converted into active rutile seeding form.

2. The method of claim 1, in which the acid is hydrochloric acid.

3 -A process for producingrutile seed for use 5 5 inf the production of titanium dioxide having rutile crystal structure, which comprises treating orthotitanic acid, containing occluded sulfates, with an alkaline alkali metal compound to form an alkali metal titanate, washing the alkali metal titanate free of sulfates, and treating the titanate with a monobasic acid in suflicient amount to completely convert the alkali metal content to the salt of the monobasic acid and to theoretically convert about 20% to 50% of the titanium content to the salt of the monobasic acid, and heating the resultant mixture, whereby the titanium content is substantially converted into active rutile Seeding form.

4. A process for preparing a rutile seeding agent for the conversion to rutile of a hydrated titanium dioxide obtained by the hydrolysis of a titanium sulfate solution, which comprises treating orthotitanic acid with an alkaline alkali metal compound to form an alkali metal titanate, and treatin the titanate with a monobasic acid in suificient amount to completely convert the alkali metal content to the salt of the monobasic acid and to theoretically convert about 20% to about 50% of the titanium content to the salt of the monobasic acid, and boiling the resultant mixture for about one hour, whereby the titanium content is substantially converted to a rutile conversion seed.

5. A process for preparing a rutile seeding agent which comprises treating orthotitanic acid with an alkaline alkali metal compound to form an alkali metal titanate, treating said alkali metal titanate with a monobasic acid in sufficient amount to completely convert the alkali metal content thereof to the salt of the monobasic acid REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,697,929 Ryan Jan. 8, 1929 1,922,328 Rhodes Aug. 15, 1933 1,932,087 Richter Oct. 24, 1933 2,029,881 Little Feb. 4, 1936 2,078,279 Richter Apr. 27, 1937 2,089,180 Bousquet et al Aug. 10, 1937 2,111,460 Rockstroh Mar. 15, 1938 2,143,851 Allan Jan. 17, 1939 2,292,507 Brooks Aug. 11, 1942 2,301,412 Keats et al Nov. 10, 1942 2,303,306 Tellmann Nov. 24, 1942 FOREIGN PATENTS Number Country Date 149,316 Great Britain June 16, 1921 405,669 Great Britain Feb. 12, 1934 463,966 Great Britain Apr. 8, 1937 533,227 Great Britain Feb. 10, 1941 OTHER REFERENCES Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. VII, page 39. 

